Distillate petroleum product and method of treating same



' in maintaining tankers, storage tanks,

Patented May 15, 1934 DISTILLATE -PETROLEUM -PRODUCT AND METHOD OF TREATING SAMIE James B. Rather, Brooklyn, Orland M. Reifl,

Jackson Heights, and Leslie 0. Beard, Jr., Brooklyn, N. Y., assignors to Socony-Vacuum, Corporation, New York, N. Y., a corporation of New York No Drawing.

16 Claims.

invention relates to distillate petroleum products, more particularly gasoline and kerosene, and to a method of and means for imparting a stability thereto with respect to color,

5 gum formation and odor, and for removing any objectionable color developed therein during storage.

Heretofore we have discovered that certain organic compounds of the nature of negative oxidation catalysts have the property of preventing or materially delaying the formation of color, gum and malodorous constituents in distillate petroleum products, particularly gasoline and kerosene. Notable-amongst these compounds are the hydroxybenzenes, especially hydroquinone and pyrogallol. Certain of these compounds,

particularly hydroquinone and pyrogall l, have the added property of decolorizing distill te petroleum products which have become discolored We have found, however, that anumber of these compounds will not function properly in the presence of water, due to the fact that they are considerably more soluble in water than in the distillate petroleum products. This characteristic materially affects the commercial value of these compounds as stabilizers and decolorizers, particularly when the treated distillates are handled in bulk, because of the difliculties involved pipe lines and delivery trucks free of water.

In accordance with the present invention, however, the decolorization and/or the stabilization of distillate petroleum productswith regard 5 to color, gum formation and odor may be readily and effectually attained regardless of the presence of water, by the use of certain water insoluble compounds we have found to be suitable for the purpose.

One of the objects of the present invention is to provide a method of and means for effectually decolorizing and/or stabilizing distillate petroleum products with respect to color, gum formation and odor in the presence of water.

Another object of the invention is to provide agents or compounds which'in the presence of water, will elfectually decolorize and/or stabilize distillate petroleum products with respect to color, gum and odor.

Another object of the invention is to provide water insoluble agents or compounds which are eifective as decolorizers and/or stabilizers of distillate petroleum products with respect to color, gum formation and odor.

Another object of the invention is to provide thoroughly mixed with the distillate to be treated,

Applicationseptember 25, 1929,

Serial No. 395,192

agents or compounds effective in removing initial or recurrent'discoloration of distillate petroleum products and for stabilizing the same as to color, odor, and the formation of gum, which agents or compounds are soluble in the distillates and insoluble in water.

A further object of the invention is to provide agents or compounds of the character referred to which are unaffected in their action by the presence of water. 05

Other objects of the invention will be apparent from the following description.

Among the compounds in the nature of negative oxidation catalysts that we have discovered are suitable for the objects set forth are the alkyl substituted hydroxybenzenes, such as the diamyl and methyl substituted hydroxybenzenes, particularly diamyl hy'droquinone and tolu hydroquinone. These compounds are formed preferably by substituting alkyl groups for some of the hydrogens in hydroxybenzenes such as hydroquincne and are substantially insoluble in water but readily soluble in'distillatepetroleum products. For example, diamyl hydroquiiioneis soluble in distillate petroleum products, such as kerosene, to the extent of one part of diamyl hydroquinone to approximately eight hundredparts of kerosene and is practically insoluble in water. Hydroquinone, on the other hand, is not assoluble in petroleum distillates, being soluble to the extent of one part of hydroquinone to approximately one hundred thousand parts of kerosene while'it readily dissolves in water to the extent of approximately six parts of liydroquinone to one hundred parts of water.

- A relatively minute amount, preferably less than 0.01% of the agent or compound may be although it will be understood that the distillate may be percolated through a mass of the compound, if desired. Preferably, however, the compound is first dissolved in a suitable solvent which is miscible in the distillate, such as an aliphatic alcohol, particularly isopropyl alcohol, in the proportion of one part of the compound to'approximately ten parts of the solvent. The resulting solution is then added to the distillate to be treat ed in minute amounts, preferably less than 0.1%. This method usually results in the compound be-- ing distributed throughout and dissolved in the distillate more readily than if it were added directly thereto.

The results of the following tests will illustrate the effectiveness of the treatment of distillate pe- I late petroleum product of the class of gasoline troleum products in accordance with our invenor kerosene which normally tends to deteriorate tion. Samples of a kerosene which had develby oxidation, as evidenced by the formation of oped a color of minus 15 Saybolt during storage color or gum therein during storage, having addwere treated with one part of compound to aped thereto a small amount of a diamyl substituted proximately 25,000 parts of the kerosene and afhydroquinone sufli cient substantially to retard ter decolorization, each of the samples was conthe aforesaid deterioration, the amyl group betacted with 20% by volume of water and the color ing substituted for hydrogen of the benzene nunoted after periods of one day and one week. The cleus. sample treated with diamyl hydroquinone after 6. A low boiling normally light colored disone day had a color of plus 13 and maintained tillate petroleumproduct of the class of gasoline this color to the time of the second reading at the or kerosene ,which normally tends to deteriorate end of a week. The sample treated with tolu by oxidation, as evidenced by the formation of hydroquinone had a Saybolt color after one day color or gum therein during storage, having added of plus 13 and after a week, a colorof plus 6. thereto a small amount of a methyl substituted Othersamples were treatedwlth hydroquinone hydroquinone suificient substantially to retard and pyrogallol to obtain comparative data. The the aforesaid deterioration, the methyl group sample treated with hydroquinone after one day being substituted for hydrogen of the benzene had a color of plus 11 Saybolt and after one week, nucleus. x the color had changed to minus 5. The sample '7. A boiling normally light colored distillate treated with pyrogallol, after one day had a color petroleum product of the class of gasoline or of plus 10 and after a week, a color of plus 2. kerosene which normally tends to deteriorate by Other samples, however, treated with hydrooxidation, as evidenced by the formation of color quinone and pyrogallol, in the absence of water or gum therein during storage, having added held their restored color of plus 11 and plus 10 rethereto a small amount of a diamyl substituted spectively, as noted above, for several months *dihydroxy benzene sufficient substantially to rewithout change. tard the aforesaid deterioration, the amyl group Diamyl hydroquinone is prepared by condensbeing substituted for hydrogen of the benzene ing amylene with hydroquinone in the presence nucleus. of sulfuric and glacial acetic acids at ordinary 8. Alowboiling normally light colored distillate temperatures, Koenig, Berichte 25, 2650 (1892). petroleum p du t f th lass f asolin or While we have thus specifically described our kerosene which normally tends to deteriorate by invention, various modifications thereof may sugoxidation, as evidenced by the formation of color claims.

2 storage by formation of varying relative proporzene nucleus. I 1

gest themselves to those skilled in the art, and or gum 'therein during storage, having added it therefore is,our intention that the invention thereto a small amount of a methyl substituted be limited only by the scope of the appended dihydroxy benzene sufficient substantially to retard the aforesaid deterioration, the methyl group HaTving thus described our invention, what we being substituted for hydrogen of the ,benzene claim and' desire to secure by Letters Patent is: nucleus.

1. A petroleum distillate product gagaarg of flf'l hemet o of stabilizing the, characteristics use as a motor fuel lying wit meof a low boiling normally light colored petroleum kerosene range normally tending to deteriorate distillate product of the class of gasoline or 'on'storage by formation of varying relative prokerosene that normally tends to deteriorate by portions of gum and color stabilized by the addioxidation, as evidenced by the formation of color tion of a' small fquantity of an alkyl substituted or gum therein during storage, which comprises hydroquinone, the alkyl group being substituted adding thereto, prior to substantial deterioration for hydrogen 'of the benzene nucleus, as aforesaid, a small proportion of an alkyl sub- 2. A petroleum distillateproduct capable of use stituted dihydroxy benzene suflicient substantialas a motor fuel lying within the gasoline-kero- 1y to retard the aforesaid deterioration, the alkyl senerange normally tending to deteriorate on group being substituted for hydrogen of the hen tions of gum and color stabilized by the addition of a small quantity of a diamyl substituted hydro- -10. The method of stabilizing the characteristics of a low boiling normally light colored quinone, the amyl group being substituted for hypetroleum distillate product of the class of gasodrogen of the benzene nucleus. V line or kerosene that normally tends to deteriorate 3. A low boiling normally light colored distilby oxidation, as evidenced by the formation of late petroleum product of the class of gasoline or color or gum'therein during storage, which comkerosene' which normally tends to deteriorate by .prises adding thereto,prior to substantial deterioxidatiomas evidenced by theformation of color oration as aforesaid, a small proportion of a or gum therein during storage, having added diamylsubstituted hydroquinone suflicient subthereto a small amount -of an alkylsubstituted stantially to retard the aforesaid deterioration, dihydroxy benzene suflicient' substantially to rethe amyl group being substituted for hydrogen tard the aforesaid "deterioration, the alkyl group of the benzene nucleus. being substituted for hydrogen of the benzene 11. The method of decolorizing a normally nucleus. light colored low boiling petroleum distillate prod- 4. A low boiling normally light colored distiluct of the class of gasoline or kerosene which 'has late petroleum product of the class of gasoline become discolored by spontaneous color formaor kerosene which normally tends to deteriorate tion during storage, which comprises adding to by oxidatio as evidencedby the formation of said discolored product a small proportion of' an color or gum therein during storage, having addalkyl substituted dihydroxy benzene suflicient to ed thereto a small amount of an alkyl substituted effect removal of a substantial proportion of the hydroquinone suflicientsubstantially to retard aforesaid discoloration, the alkyl group being subthe aforesaid deterioration, the alkyl group being stituted for hydrogen of the benzene nucleus. substituted for hydrogen'of the benzene nucleus. 12. The method of decolorizing a normally light A low boiling normally light colored disti1-- colored low boiling petroleum distillate product mo els of the class of gasoline or kerosene which has become discolored by spontaneous color forma tion during storage, which comprises adding to said discolored product a small proportion of an alkyl'substituted hydroquinone sumcient to effect removal or a substantial said discoloration, the alkyl group being substituted for hydrogen of the benzene nucleus.

13. The method of decolorizing a normally light colored low boiling. petroleum distillate product of proportion oithe aforethe class of gasoline or kerosene which has bee come discolored by spontaneous color formation during storage, which comprises adding to said discolored product a small proportion of a diamyl substituted hydroquinone sutficient to effect removal of a substantial proportion of the aforesaid discoloration, the amyl group being substituted for hydrogen of the benzene nucleus.

14. The method of decolorizing a normally light colored low boiling petroleum distillate product of the class of gasoline or kerosene which has become discolored by spontaneous color formation during storage, which comprises adding to said discolored product a small proportion of a methyl substituted'hydroquinone suflicient'to effect removal of a substantial proportion of the aforesaid discoloration, the substituted for hydrogen'of the benzene nucleus.

15. The method of decolorizing a normally light colored low boiling petroleum distillate product of the class of gasoline or kerosene which has be-= come discolored by spontaneous color formation during storage, which comprises adding to said methyl group being discolored product a small proportion of a diamyl Y the amyl group being sub- 16. The method of dec'olorizing a normally light colored low boiling too 

